Quenching oil compositions



QUEN CHIN G OIL COMPOSITIONS Carl Frederick Zimpel, East Alton, -Ill., assignor to Shell Development Company,

tionof Delaware No Drawing. Application July 27, 1956 Serial No. 600,390

10 Claims. (Cl. 14829) This invention relates to improved quenching oil compositions for use in the; metallurgical industries and to the method of quenching metals therewith: V

In the process ofhardening metals such as steels, it is common practice to use as the quenching medium water, oil or compressed air, according to the type of steel. Recently salts or aqueous solutions of salts have also been used for this purpose but these have the disadvantage that theysolidify o-r depositsolids on cooling to room temperature. Fatty oils, especially rapeseed oil are used as quenching oil, but these have been'gradually superseded by mineral quenching oils. It has also been proposed to harden and temper steels using baths containing naphthalene monoor di-sulphonic acids or salts thereof or anthracene monoor di-sulphonic. acids or salts thereof. Sulphonic .acids or their saltsare mixed with water or oil to form the treating bath andthe oils generally used are linseed oil, fatty substances.

Quenching compositions of the above types are de-,

fective in a number of respects among which are that water quenching causes stress and strain in the steel which tend to warp and crack thesteeL. Oil quenching is expensive. because the oil deteriorates rapidly in 'use and must be refined, fortifiedl'or. be continuously replaced with fresh oil.

It has now been discovered that an excellent thermally stable quenching composition for metals suchas steel and steel alloys can be provided Which'comprises' a mineral oil base containing a critical amount-within the range of from about 1.75% to about 3.0% by weight and preferably between 2.0% and 3.0% of an artificial resin prepared by polymerizing cycloalkenehydrocarbons or lower polymers thereof with linolenic acid oils and their derivatives. t

The cycloalkene hydrocarbons of which preferred are the cycloalkadiene hydrocarbons such as cyclopentadiene hydrocarbons, can be obtained by cracking'of petroleum hydrocarbons, from domestic gas production or from coal tar industry. Cyclo-alkene hydrocarbons include cyclopentadiene, dicyclopentadiene, lower polycyclopentadienes, methyl cyclopentadiene and the like.

The linolenic acid oils and derivatives thereof which are used in the copolymeric resin include products having an iodine value of around 100-150 and containing at least 35% linolenic acid (diene)' not more than 10% linolenic aci d (triene) and not more than 25% saturated fatty acids. Such oils can be exemplified by soybean oil, perilla oil, cottonseed oil, hempseed oil, sunflower oil', walnut'oil, poppyseed oil, sesame oil, maize oil, their acids and mixtures thereof.

The reaction can be conducted with or without the use New .YorlgN. Y., a corporacotton seed oil and other .from 5% to 20%,

'diene with soybean oil, or

fonate, Y waxbenzene sulfonate,

2,866,729 Patented Dec. 30, 1 958 of a catalyst. The catalysts include salts of heavy metals such as nickel' naphthenate or halides of amphoteric metals such as tin tetrachloride or bromide or iodide, or chlorides of antimony, bismuth and aluminum, as well as boron fluoride and dihydroxy fiuoboric acid.

The temperature of the reactions can vary from about 50 C. to above 300 C. The reaction time varies depending upon the reactants, temperature, oil-solubility, and viscosity or physicalstat e of the final product. In general, the reaction time varies from 2 to 24 hours.

The 'copolymer can be modified by introducing into the copolymer small amounts of various terpenic materials such as cyclic terpenes including dipentene, terpenolene,-limonene, camphene, bornylene, or turpentine and pine oil and derivatives thereof-.-

The amounts of cycloalkene hydrocarbons and linolenic acid oils and derivatives thereof used to form the polymer can be varied from 5% to and from 95% to 5%, respectively. the reaction mixtures, h y arepresent in amounts of based on the cycloalkene hydrocarbon.

Copolymersof this type can be prepared by the method described in the Journal of the American Oil Chemists Society, volume 3-November 1954, page 543. Examples of such copolymers include copolymers of cyclopentaperilla oil, or poppyseed oil, or copolymers of-dicyclopentadiene with soybean oil or mixtures of soybean oil and dipentene. A particularly preferred copolymer is sold commercially by Spencer Kellogg and Sons under the trade name Cykelsoy being a dicyclopentadiene soybean oil condensation prod-' Viscosity (Gardner-Holdt Z2 Acid number 6.2 Color (Gardner) 11 Specific gravity 0.9705 Saponification number 168.3 Iodine number 129.7

Otherv examples of resinous "additives used in uenchingcompositions of this invention are prepared as follows:

Example I.About equal'arnounts of cyclopentadiene and soybean oil were reacted atsabout 250 'C. in the presence of dihydroxyfluobo-ric acid catalyst forabout 3 hours. The polymer was oil'soluble Example II.The procedure of Example I was followed using perilla oil instead of soybean oil.

Example III.The procedure of Example I was followed-using poppyseed oil instead of soybean oil.

Other suitable resins prepared by the method described I above include copolymers of dicyclopentadicue/cottonseed oil, terpolymer of dicyclopentadiene/soybean/perilla oils and methylcyclopentadiene/ soybean oil .copolymer.

Minor amounts of from about 0.1 to 2% of secondary additives can beused in compositions of this invention.

Particularly preferred are dispersants which can be of the ash-forming and/or ashless type .dispersants such as l metal sulfonates or phenates or ashless polymeric dispersants. The ,sulfonates and phenates include alkali and alkaline earth metal (Na, Ca, Ba) petroleum sulfonate, alkyl phenate, dibutyl-phenol sulfide, octylphenolformaldehyde condensation, product and thelike. The ashless dispers'ants include oil-soluble nitrogen-containing polymeric dispersantsisuch as Du Ponts PL-164A,

LOA564, and LOA565 which are described in U. S..P.at-'

If terpenic materials are introduced into alkyl naphthalene sul- 3 ents 2,660,044, and 2,734,496 or Rohm and Haass ashless dispersant Acryloid 966" described in Petroleum Engineer, May 1956, page C-32. Other specific alkylmethacrylate ashless dispersants are vinyl pyridine/alkyl methacrylate polymers, vinyl pyrrolidone/alkyl methacrylate polymers such as 2-methyl-5-vinyl pyridine/ mixed lauryi and octadecyl methacrylates, vinyl pyrrolidone/lauryl methacrylate copolymers and the like.

The oils whichcomprise the mhjor. proportion of the quenching compositions are mineral= oils obtained as distillates from various types of crude oil such as paraffinic, asphaltic or mixed base crudes. The oils should have a flash point of above 300' F. and a SayboltUniversal viscosity at 100 F. of above 80 seconds and preferably from: about 100 to about 200 seconds. Blends of different petroleum oils or mixtures of petroleum and fixed oils such as palm, rapeseed, and castor oils can be used:

The following compositions illustrate the invention:

Composition A: 1 Percent Cykelsoy 1 2 Mineral oil (100 SUS, 100 F.) 98

Composition B:

Cykelsoy 3 Mineral oil (100 SUS,. 100 F.) 97

Composition Cz 1 Cykelsoy-Speneer Kellogg and Sons Product, as defined in column 2, lines 28 to 40.

Hardening metals such as steel by quenching operation can be done by any suitable means well known in the art. In essence the method of hardening steel by quenching comprises heating the metal to a temperature above its Table I Bright Quench S-Second Hot-Wire Rating (i=clean, Quench Quench 10=very dirty), Composition Test Test Days Speed, Rating g Percent (I max.)

Mineral oil (100 SUS 100 F) 15 320 10 CompositionA 29 720 3 3 4 Composition B 29 710 3 3 3 4 Composition U (mineral oil +4%Acryloid 710'") 410 10 10 Composition V (mineral oil +63% santodex 380 10 Composition W (mineral oil +1 Cykelsoy) 392 Composition X (mine al 011 +1 Cykelso 449 Composition Y (mineral oil +40% Cykelsoy) 671 Composition Z (mineral oil +571, eopolymer oi cyclopeuta'liene and a vegetable oil having an iodine number above 150 and above 35% linolenic acid) l Acryloid 710=poiyrnerization product of esters of methacrylic acid and higher fatty alcohols described in U. S. Patent 2,712,726.

1 Santodex=copolymers of Cz-Cn olefin and styrene.

Compositions C, D and E of this invention when tested 1 as described above give substantially the same results as critical temperature and thereafterquenching the metal by immersion in a present invention.

quenching oil composition of the The meaning of hardening steel by quenching is .well understood inthe art as evidenced by reference to Lubrication for September 1951, or Forbes text on Lubrication of Industrial and Marine Machinery" (second edition), chapter 31.

The effectiveness of compositions of this invention as quenching media is demonstrated by the data presented in Table I in which the test compositions were subjected to the S-second quench test, and the beaker oxidation test. The 5-second quench test is described in Petroleum, January 1945, page 17.

The hot-wire quench test is a measure of the" maximum amount of energy which a hot wire will dissipate to an oil. The maximum amount of energy which a hot wire will dissipate to increasing the current hrough the wire continuously until burnout occurs. be calculated fromvoltage and current measurements:

where I=current andR is the resistance of-the wire.

The bright quench test rating is a measure of the amount of deposits formedon the surface of the metaltest specimen after it has been quenched in an oil that has been previously aged at 250 F. The specimens are rated 1 for cleanand 10 for dirty;

the hot-wire quench test.

the oil may be determined by The maximum energy can then obtained with Compositions A and B.

I claim as my invention:

1. A quenching oil composition consisting essentially of a major amount of a mineral oil having a viscosity of from to 200 SUS at 100 F. containing from about 1.75% to about 3.0% of an oil-soluble copolymer obtained by reacting a cycloalkadiene hydrocarbon and a linolenic acid oil having an iodine value between 100 and for 2-24 hours at a temperature of from 50 C. to 300 C.

2. The composition of claim 1, wherein the cycloalkadiene hydrocarbon is cyclopentadiene.

3. The composition of claim 1, wherein the cycloalkadiene hydrocarbon is dicyclopentadiene.

4.'A quenching oil composition consisting essentially of a major amount of mineral oil having a viscosity of. about 100 SUS at 100 F. containing from about 2% to about 3% of an oil-soluble copolymer obtained by reacting dicyclopentadiene and soybean oil for about 3 hours at about 250 C. until the viscosity of the copolymer-is about Z2 (Gardner-Holdt).

5. A quenching oil composition consisting essentially of a major amount of mineral oil having a viscosity of about 100 SUS at 100 F. containing from about 2% to about 3% of an oil-soluble copolyrner obtained by reacting dicyclopentadiene and soybean oil for about 3 hours at about 250 C. until the viscosity of the copolymer is about Z2 (Gardner-Holdt), and from about 0.1% to 2% of a dispersant selected from the group consisting of oil-soluble metal sulfonate, metal phenate and oilsoluble nitrogen-containing polymeric compound.

6. The composition of claim 5, wherein the dispersant is an oil-soluble calcium petroleum sulfonate.

7. The composition of claim 5, wherein the dispersant is lauryl' methacrylatediethylamino ethyl methacrylate copolymer.

8. Amethod of hardening steel comprising heating such steel to a temperature above its critical temperature and thereafter quenching such steel by immersion in the (References on following page) References Cited in the file of this patent UNITED STATES PATENTS Horst Feb. 1, 1944 Gerhardt Oct. 30, 1945 5 Mapes Oct. 18, 1949 

1. A QUENCHING OIL COMPOSITION CONSISTING ESSENTIALLY OF A MAJOR AMOUNT OF A MINERAL OIL HAING A VISCOSITY OF FROM 100 TO 200 SUS AT 100*F. CONTAINING FROM ABOUT 1.75% TO ABOUT 3.0% OF AN OIL-SOLUBLE COPOLYMER OBTAINED BY REACTING A CYCLOALKADIENE HYDROCARBON AND A LINOLENIC ACID OIL HAVING AN IODINE VALUE BETWEEN 100 AND 150 FOR 2-24 HOURS AT A TEMPERATURE OF FROM 50*C. TO 300*C. 